Process for making silicon nitride whisker

ABSTRACT

Silica powder or a mixture of silica powder and silicon nitride whisker is heated at a temperature ranging from 800 DEG  C. to 1,700 DEG  C. in a gas mixture of ammonia gas (NH3) and hydrocarbon gas (CmHn) so as to produce silicon nitride whisker. The gas mixture flows at the rate of 10 mm/sec or less. The NH3/CH4 ratio of the ammonia to the hydrocarbon, expressed as CH4, ranges from 0.5:1 to 2000:1 by volume. The silica powder is preferably mixed with at least one of six catalysts: transition metals; alkali metals; alkaline earth metals; halides of transition metals; halides of alkali metals; and alkaline earth metals. One mol part of the silica powder is mixed with 0.001-1.0 mol part of the catalyst.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a process for making silicon nitride whiskers.

2. Description of Related Art

Japanese Patent No. 838,421 discloses a method for making silicon nitride whiskers by mixing amorphous silica powders, to which fluoride, acidic fluoride or silica-fluoride are attached, with carbonaceous powders so as to produce a mixture and heating the mixture in a nitrogen atmosphere at a temperature of 1,300° C. to 1,600° C.

In the conventional process for preparing silicon nitride whiskers, silica powders are mixed with the carbon powders in a solid-solid reaction manner. If they are not properly mixed, no uniform reaction takes place. As a result, diameters of the produced whiskers vary. Even silicon powders are sometimes are produced in admixture with the whiskers.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a process for making silicon nitride whiskers having substantially uniform diameters with a good yield, excluding any silicon nitride powders.

According to this invention, a powder of silica or a silica precursor is heated at a temperature ranging from 800° C. to 1,700° C. and preferably from 1,200° C. to 1,700° C. in a gas mixture of ammonia gas (NH₃) and hydrocarbon gas (C_(m) H_(n)) so as to produce silicon nitride whiskers. Examples of the hydrocarbon gas are methane, ethane, propane and acetylene gases. The bulk specific gravity of the silica powders is preferably 400 g/l or less and ranges from 50 g/l to 200 g/l for the best results.

The gas mixture flows at a flow rate of 10 mm/sec or less and preferably ranging from 10 mm/sec to 0.1 mm/sec. For the best results, the flow rate ranges from 5 mm/sec to 0.1 mm/sec. If the flow rate is larger than 10 mm/sec, silicon nitride powders could be partly produced in admixture with silicon nitride whiskers.

The NH₃ /CH₄ ratio of the ammonia to the hydrocarbon, expressed as CH₄, ranges from 0.5:1 to 2000:1 by volume and preferably from 20:1 to 1000:1 by volume or from 0.1/100 to 5/100. If the ratio (NH₃ /CmHn) is lesser than 0.5:1 by volume, the partial pressure of NH₃ becomes too low, causing the reaction to proceed too slowly. If the ratio is larger than 2,000:1 by volume, the effect of addition of CH₄ cannot be obtained.

The silica powders are preferably mixed with at least one of six catalysts: transition metals; alkali metals; alkaline earth metals; halides of transition metals; halides of alkali metals; and alkaline earth metals. All six catalysts can be used in combination. One mol part of the silica powders is preferably mixed with 0.001-1.0 mol part of the catalyst. In such a case, silicon nitride whiskers can be stable and quickly produced.

Basically, silicon nitride whiskers are produced according to the following reaction scheme (1):

    3SiO.sub.2 +4NH.sub.3 =Si.sub.3 N.sub.4 +6H.sub.2 O        (1)

The partial pressure of H₂ O generated during the reaction is reduced in accordance with the following reaction (2):

    mH.sub.2 O+CmHn=mCO+(m+n/2)H.sub.2                         (2)

Reduction in the partial pressure of H₂ O in accordance with the reaction scheme (2) may smoothly proceed in accordance with the reaction scheme (1).

The reaction is carried out at a temperature in the range from 800° C. to 1,700° C. and preferably 1,200° C. to 1,700° C. If the temperature is lower than 800° C., on the one hand, the reaction does not substantially proceed in a desired manner. If the temperature is higher than 1,700° C., on the other hand, SiC is partially produced so that the purity of the produced silicon nitride whiskers decreases.

In order to accelerate production of silicon nitride whiskers, a mullite or kaolinite substance such as SiO₂, Al₂ O₃ or a compound thereof can be admixed into the reaction mixture.

The present invention will be further described below by way of examples. In place of silica powder (SiO₂) only, a mixture of silica powder and silicon nitride whisker (Si₃ N₄) can be used as a starting material. If 10% or more of silicon nitride whisker is mixed with 90% or less of silica powder, the diameter of the produced silicon nitride whisker becomes large.

EXAMPLE 1

3 grams of silica powders having an average diameter of 0.02 microns was set in a boat made of silicon nitride. The boat was inserted into an alumina process tube. A gas mixture of ammonia gas (NH₃) and hydrocarbon gas (C₃ H₈) was introduced at the flow rate of 1 mm/sec under standard conditions, causing a turbulence of the mixed gas in the process tube, while the silica powders were heated at 1,400° C. for 4 hours.

The resulting product was analyzed to determine its structure by a well-known X-ray analysis and SEM. Table 1B below shows the results of analysis.

EXAMPLES 2-6

In Example 2, 0.05 mol part of NaCl was added to one mol part of the silica powders (3 grams) having an average diameter of 0.02 microns so as to make a first mixture. Acetone was added to the first mixture and then blended in an agate mortar so as to make a second mixture. After the second mixture was dried, the procedures followed substantially the same procedure as in Example 1 with the exception that the heating temperature was 1,450° C.

In Example 3, 0.5 mol part of NaF was added to 1 mol part of silica so as to make a mixture. After that, the procedures followed substantially the same procedure as in Example 1.

In Examples 4 to 6, the procedures followed substantially the same procedure as in Example 1 with the exceptions shown in Table 1A.

COMPARATIVE EXAMPLES 1-4

The procedures followed substantially the same procedure as Example 1 with the exceptions shown in Table lA. The results of the analyses are shown in Table 1B below.

                                      TABLE 1A                                     __________________________________________________________________________     Process Conditions                                                                                   Gas                                                                       Type of                                                                             Flow Heating                                                                             Heating                                               Added                                                                               Mixture                                                                             mixed                                                                               Rate Tempera-                                                                            Time                                                  Material                                                                            Ratio                                                                               gas  (mm/sec)                                                                            ture (°C.)                                                                   (hr)                                           __________________________________________________________________________     Example                                                                         1     --   --   C.sub.3 H.sub.8 +                                                                   1    1400 4                                              2      NaCl 0.05 NH.sub.3                                                                            5    1450 4                                              3      NaF  0.5       5    1400 4                                              4      Fe   0.001     5    1400 4                                              5      MgCl.sub.2                                                                          0.005     5    1400 4                                              6      FeCl.sub.3                                                                          0.003     5    1350 4                                              Comparative                                                                    Example                                                                        1      --   --   C.sub.3 H.sub.8 +                                                                   15   1450 4                                              2      NaCl 2    NH.sub.3                                                                            5    1450 4                                              3      NaCl 0.05      5    1700 4                                              4      NaCl 0.05      5     750 4                                              __________________________________________________________________________      *The mixture ratio denotes the ratio of the mol part of the added materia      to 1 mol part of silica (SiO.sub.2).                                           *The NH.sub.3 /C.sub.3 H.sub.8 ratio is 1.32/100 by volume.              

                  TABLE 1B                                                         ______________________________________                                         Characteristics of the Product                                                         X-ray analysis                                                                             SEM observation                                                    Indentification                                                                            (micron meters)                                                    Phase       Length    Diameter                                         ______________________________________                                         Example                                                                               1      alpha-Si.sub.3 N.sub.4                                                                       20-50   0.5-1.0                                    Example                                                                               2         "          20-50   0.5-1.0                                    Example                                                                               3         "          20-50   0.5-1.0                                    Example                                                                               4         "          20-50   0.5-1.5                                    Example                                                                               5         "          20-50   0.5-1.0                                    Example                                                                               6         "          10-50   0.1-1.0                                    Compa- 1      alpha-Si.sub.3 N.sub.4                                                                       No whiskers are produced.                          rative 2      Amorp. SiO.sub.2                                                                             Many glass balls are                               Example       >> alpha-Si.sub.3 N.sub.4                                                                    produced.                                                 3      SiC           5-50    0.1-1.5                                                  >> alpha-Si.sub.3 N.sub.4                                               4      Amorph. SiO.sub.2                                                                            No reaction proceeds.                              ______________________________________                                    

As will be apparent from Tables 1A and 1B above, it has been found that the produced silicon nitride whiskers have uniform length and diameters with an excellent yield, for example, such as 75-80 % in Examples 1 to 6 embodying the present invention. 

What is claimed is:
 1. A process for producing silicon nitride whiskers, said process comprising:providing a powder consisting essentially of silica; contacting said powder with a gas mixture consisting essentially of ammonia and hydrocarbon gas, the NH₃ /CH₄ ratio of said ammonia to said hydrocarbon, expressed as CH₄, ranging from 0.5:1 to 2000:1 by volume; and heating said powder in said gas mixture to a temperature of 800° C. to 1700° C. while said gas mixture is supplied at the rate of 10 mm/sec or less; wherein the silicon nitride whiskers are produced according to the following reaction:

    3SiO.sub.2 +4NH.sub.3 =Si.sub.3 N.sub.4 +6H.sub.2 O

and the H₂ O generated during the reaction is removed from said gas mixture in accordance with the following reaction:

    mH.sub.2 O+CmHn=mCO+(m+n/2)H.sub.2.


2. A process as claimed in claim 1, wherein said gas mixture flows at the rate of 5 to 0.1 mm/sec.
 3. A process as claimed in claim 1, wherein said gas mixture flows at the rate of 10 to 0.1 mm/sec.
 4. A process as claimed in claim 1, wherein the heating temperature ranges from 1200° C. to 1700° C.
 5. A process as claimed in claim 1, wherein the NH₃ /CH₄ ratio ranges from 20:1 to 1000:1.
 6. A process as claimed in claim 1, wherein the powder is mixed with at least one catalyst selected from the group consisting of: transition metals, alkali metals, alkaline earth metals, halides of transition metals, halides of alkali metals and alkaline earth metals.
 7. A process as claimed in claim 6, wherein one mol part of the powder is mixed with 0.001-1.0 mol part of the catalyst.
 8. A process as claimed in claim 1, wherein the powder is set in a boat made of silicon nitride and wherein the boat is inserted in a process tube made of alumina.
 9. A process as claimed in claim 6, wherein the powder and the catalyst are set in a boat made of silicon nitride and wherein the boat is inserted in a process tube made of alumina.
 10. A process as claim 8, wherein the powder has an average diameter of 0.02 micron meters or less.
 11. A process for producing silicon nitride whiskers, said process comprising:providing a powder mixture of silicon nitride whiskers and a powder consisting essentially of silica; contacting said powder mixture with a gas mixture consisting essentially of ammonia and hydrocarbon gas, the NH₃ /CH₄ ratio of said ammonia to said hydrocarbon, expressed as CH₄, ranging from 0.5:1 to 2000:1 by volume; and heating said powder mixture in said gas mixture to a temperature of 800° C. to 1700° C. while said gas mixture is supplied at the rate of 10 mm/sec of less; wherein the silicon nitride whiskers are produced according to the following reaction:

    3SiO.sub.2 +4NH.sub.3 =Si.sub.3 N.sub.4 +6H.sub.2 O

and the H₂ O generated during the reaction is removed from said gas mixture in accordance with the following reaction:

    mH.sub.2 O+CmHn=mCO+(m+n/2)H.sub.2.


12. A process as claimed in claim 11, wherein said gas mixture flows at the rate of 5 to 0.1 mm/sec.
 13. A process as claimed in claim 11, wherein said gas mixture flows at the rate of 10 to 0.1 mm/sec.
 14. A process as claimed in claim 11, wherein the heating temperature ranges from 1200° C. to 1700° C.
 15. A process as claimed in claim 11, wherein the NH₃ /CH₄ ratio ranges from 20:1 to 1000:1.
 16. A process as claimed in claim 11, wherein said mixture is mixed with at least one catalyst selected from the group consisting of: transition metals, alkali metals, alkaline earth metals, halides of transition metals, halides of alkali metals and alkaline earth metals.
 17. A process as claimed in claim 16, wherein one mol part of the powder is mixed with 0.001-1.0 mol part of the catalyst.
 18. A process as claimed in claim 11, wherein the mixture is set in a boat made of silicon nitride and wherein the boat is inserted in a process tube made of alumina.
 19. A process as claimed in claim 16, wherein the mixture and the catalyst are set in a boat made of silicon nitride and wherein the boat is inserted in a process tube made of alumina.
 20. A process as claim 18, wherein the powder has an average diameter of 0.02 micron meters or less. 